Process for hydrocarbon oil conversion



Nov. 15, 1932. c. P. DuBBs 1,888,028

PROCESS FOR HYDROOARBON OIL CONVERSION Filed April 4, 1.927 2 Sheets-Smet 1 Nov. 1s, 1932. Q P, DUBBS 1,888,028A- PROCESS FORHYDROCARBON OIL CONVERSION into lighter oils, and more Patented Nov. 15, 1932 UNITED STATES PATENT A'ol-r-lca CARBON P. DUBBS, OF WILMIHTE, ILLINOIS, ASSIGNOB TO UNIVERSAL OIL PRODUCTS COMPANY, F CHICAGO, ILLINOIS, A

CORPORATION OF SOUTH DAKOTA PROCESS FOR HYDROCARBON OIL CONVERSION Application tiled April '4,

This invention relates to improvements in the conversion of heavier hydrocarbon oil particularly into products having high anti-knock properties, or products containing substantial amounts of aromatic andunsaturate compounds'.

More particularly, the invention relates to a process wherein the oil is treated in direct contactwith combustion gases whereby it is vaporized and converted, and wherein theconstituent gases of the combustion assist in the reaction for the production ofthe hydrocarbons of the characteristics desired.

I am aware that the treatment of hydrocarbon oils in direct contact with combustion gases has been considered in the prior art, but the processes which have attempted to utilize this methodofconversion have not had the advantages which characterize lthe present invention, i. e., fiexibility and the elimination of' the-severe conditions of temperature to which the oil was subjected.

To operate this type of process without an extremely high proportion of loss in fixed gases and coke, and at the same timeto obtain the maximum obtainable .proportion of products having the desired boiling point and characteristics, it is necessary that the conditions of operation of the process be regulated toa .nicety, and particularly that the degree of heat and temperature to which theoil is subjected in contact with the combustion gases be so regulated that a relatively mild condition exists, while at the same time the oil and combustion ases are subjected to necessary heat for as ong a time as is necessary to produce the degree of conversion desired without utilizing obnoxious tempera-l tures. j

These features are present in the process o'f the invention as will appear more clearly from the following description. l

It is understood that the process object of the invention may be carried out in a number of ways and in a-variety of apparatus, but to permit a clear understanding of the invention, I have illustrated in the accompanying drawings two formsof apparatus in which the o process may be carried out.

1 is a diagrammatic drawing, partly in 1927. S'crzlal N0. 180,687.

Y effected and from which the hot combustion gases pass through flue 4 provided in the upper portion of bale wall or partition 5, into reheatin-g chamber 6. -In preheating chamer 6 is positioned a preheating coil 7', through which the oil to be treated may be passed, as hereafter described. The combus tion gases, after passing over said preheating coil 7 in the preheating chamber 6, where they arefsomewhat lowered in temperature,

pass out through iue 7 into the lower portion of the third compartment 8 of the furnace, maintained entirely separate from the other compartments, except for the iiue 7 through the medium of a separating wall or artition 9. The separating wall 9 is preferably made of radiating material so that a portion of the heat of the combustion gases passing through the preheating chamber 6 is radiated into the chamber 8 through the wall 9. It is understood that the characteristics of the material of which the wall'is made and the thickness of the wall, 'may be changed so that the amount of heat radiated through said wall can be controlled.

The material to be treated, which may be crude oil or any fraction thereof or which ma be a paste-like mixture of solid hydrocar on-containing material, such as powdered coal, coal tar and the like, with aAcon- Y 15, controlled by valve 16 which is preferably below conversion temperature, and vthen passed through transfer line into an injecting nozzle or perforated pipe 17, positioned in the upper part of the chamber 8. The injector or perforated pipe 17 may be of any desired con- Y struction, and the injection of the raw oil may be confined to one point of the chamber or may be divided over the length of the chamber 8 by extending the injector 17 through stantially liquid form at the temperature re- 22 and through line 23, controlled by valve 24,l

wardly quired, and will vaporize only Whenit 1s injected into the chamber 8.

, In said chamber 8, the oil sprayed down? through injector 17 comes in contact with the ascending combustion gases entering said chamber through iue 7. The gases7 and the oil are thus brought into intimate contact, the oil is vaporized and receives the heat required for conversion from the com-` busti'on gases in the chamber as wellas from the radiating wall 9.

The hydrocarbon vapors, non'condensible gases and combustion gases from the heating chamber 8, pass off the top of the chamber through vapor line 18 controlled by valve 19 through which they are discharged into a. reaction chamber 20. In the reaction chamber the reaction is completed and the heavier liquid and solid products of the reaction separate and are entrapped. a l

The heavy liquid products, if such are made, are v'thdrawn, preferably continuously from the reaction chamber 20, through one or more of the lines 21, controlled by valves and passed to storage or to other treating zones. Or, these liquid products" may bereturned to the heating coil 7 and heating chamber 8 for retreatment through line 25,

in which is interposed ump a and valve 26, which line is connecte with the main charging line 14. The vapors and gases separated in the reaction chamber pass' off through vapor line 2 7 controlled .by valve 28 and arey directed into dephlegmatin column 29, which is provided with suita lef'fractionating means, such as bubble trays, plates, or the like, wherein the vaporized products of'reaction undergo fractionation. The fractiona- Y cooling mediums.

be assisted by? introducing therein `For instance, all or any regulated portion of the raw oil from pump tion may j 11 can be directed into the top of the dephlegmator 29 through line 30, controlled by valve 31 instead of passing directly to the heating 65 voil may be passed direc ortion of the raw tubes through line 12, or a y' to the heating relatively the dephlegmator.

The reflux condensate and the preheated raw oil which does not vaporize in the dephlegmator are withdrawn from the bottom thereof through the line 32 connected to line 33,-which latter is controlled by valve 34, connected at its other end with main charging line 14, whereby said condensed products may be returned to the system for retreatment. A pump 35 is interposed in by-pass lines 36 and 37 controlled by valves 3 8 and 39 and connected to the reflux line 33, whereby said pump may be utilized to return the'oil from the dephlegmator to theheating coil. The line 3 2 may also be provided with a branch 40, controlled by valve 41, whereby any portion of, or all, the oil from the dephlegmator may be withdrawn from the process. v

The vapors which have not been condensed ein the dephlegmator 29 pass out therefrom through vapor line 42, controlled by valve 43, thence into condenser 44, from which the condensed and uncondensed products are directed into receiver through line 46, controlled by valve 47. The receiver is provided with gas releaseline 48 controlled by valve 49 and the liquid drawoif 50, controlled by valve 51. j- If desired, a portion of the liquid products collected in receiver 45 may be returned to the dephlegmator 29 as a cooling agent through line 52, in which may be interposed valve 53, pump 54 and valve 56.

As a further feature of the invention, a portion of the combustion gases evolved in the combustion chamber 2 of furnace 1 may be withdrawn from the furnace, after the have travelled therethrough for some lengt and 3-` For instance, this can be eifected by draw;

ing oi a portion ofthe gases of combustion from the end of the combustion chamber 2 opposite that where the burners are positioned, and as illustrated in the drawings, from the topr of chamber 2 through flue 57 on which is interposed a as pumping means such as a fan 58, where y this portion of cooler gasy is returned into the hottest com ustion gases in Ychamber 2. In this manner it 1s possible to regulate. accurately, a

by means of the mixture of the relatively c'older gas in a controlled hotter gas' of combustion, the temperature of the latter, as well as the composition of the combustion gases through the various parts .of the furnace.

In this manner, by combining the control of the temperature and composition of thc combustion gases through therecirculation of a portion thereof through flue 57 with the control of the amount of heat radiated through the partition 9 Iand that given to the oil in amount Ywith the the preheating coil 7 it' is possible to control accurately the temperature and the composition of the combustion-gases entering the heating chamber 8 and coming in contact with the oil which is atomized therein, so that the desired results may be produced.

As a further feature ofhmy invention, to combine the proper time element under which the materials undergoing reaction' are maintained under proper temperature with the regulation of said temperature, the mixture of combustion gases and vapors andiincondensible gases produced in the heating chamber 8 and Withdrawn therefrom, are returned, preferably in a continuous manner, to said chamber in a local cycle, for instance, as shown in the drawings through circulating line 59, controlled by valve and on Which is interposed the circulating vapor or gas pump of 'fan 61. A

By controlling the circulation of the vapors leaving the heating chamber 8 by valves 19 and 60, I am able to control to a nicety the length of time during which the oil is subjected to the proper temperature and treatment in contact with the combustion gases.

Although I haveshown in the drawings that portions of the combustion gases produced in combustion chamber 2 may be Withdrawn from the top ofthe combustion chamber and returned to the hottest zone of combustion near the burners 3, it is understood that the point at which apart of said gas may be withdrawn for recirculating can be varied according to the conditions of operations and result desired. For instance, the flue 57 may be connected to the top of the preheating chamber 6 or to any point in the path of the combustion gases instead of being connected to the top of the chamber 2.

In the same manner the point to which the vapors and combustion gases, Withdrawn from chamber 8 are returned may be varied,

but the are preferably returned to such a pomtvo this chamber that the returned mixture of vapors and combustion gases has to pass again, during its recirculation, through the length of the heating chamber 8 for better eiiciency of the heating process.

It can be seenthat by means of the process objectof the invention the `oil can be subjected to the treatment of the combustion gases in intimate mixture therewith at such temperature as is best to produce the desired results. The composition of the gas in contact with the oil, and particularly the amount of carbon monoxide present in said gas will be governed by the degree of incomplete combustion of the fuel consumed andthe rate Y of recirculation of the fiueV` gases.. The temperature to which the oil'is subjected will also be governed by the amount of Hue-gas circulated in the combustion chamber as Well as the degree of convection and radiation into coil 7 and through partition 9 so. that no portion of the oil is subjected to a temperature higher than-desired. Furthermore,the

circulation of the oil vapors, ue ases and the oil isv subjected when discharged into.,`

the combustion `gases in heating chamber 8.

As another lfeature of the invention the temperature to which the loil is' subjected in the heating chamber 8 is dependent upon -t-he condition of the gas, and' particularly the content of carbon monoxide in said gas. -In some instances, it may be desired to maintain the temperature in this heating chamber 8 sufficiently high to produce in said chamber A'a-substantial conversion of the oil into gasoline which I ind readily unites with the carbon monoxide to form anti-knock compounds. Any one .skilled in the artl will understand that different oils will not .react at the same temperature to the same degree, nor that the different fractions of anfoil will react 4at the same temperatures, so that the best conditions suited to the oil being treated will be determined preferably by making a pilot run with the oil being treate The pressure maintained on the system or on the' various parts thereof will depend.

upon the characteristics of the material treated, and while I consider` maintaining upon `the 'preheating coil 7 a lsuperatmospheric pressure which Will prevent substan-l tial vaporization of the oil therein under the temperature used, the'balance of the system from the heating chamber 8 on may be preferably operated under atmospheric pressure.

Vhen it is necessary, to assist in producing draft for the combustion in the furnace and motion of the vapors and gases through the system, a vacuum pump may be connected to any desired point thereof, for instance,f it may be connected to the receiver 45 or to the outlet of thecondenser 44.

While I have described heretofore a method suitable to carry out my invention under ateratmos heric ressure. yarticularl for inn 1 u stance, when production of aromatlcs 1 s de- Willremain the same, the apparatus to carry it out may be somewhat modified, and I have shown in Figs. 2'and 3 a 'suitable modified sired. While the principle of the invention trated'in Figs. 2 and 3 other parts than those which have to be substituted for the furnace and piping directly connected therewith in Fig. 1, the balance of the system may be the .same as that illustrated in Fig. 1, or of any other suitable type.

Referring toFigs. 2 and 3, the furnace 101 comprises a combustion chamber 102 heated by burners 103. The combustion gases evolved in said chamber ass through opening 104 above a separating wall 105, into convection chamber 106. The convection chamber 106 is preferably circular such as shown in section in Fig. 3. Inside said convection chamber 106 and concentrically dis,-

protected by a refractory material at the inside and outside, such as shown respectively at l110 and 111. This material is preferably of such characteristics as will radiate heat so that a portion of the heat contained in the combustion gases formed inl chamber 102 and passing through `chamber 106 around chamber 107 will radiate from the former to the latter. If metal can be used for chamber 107 which will resist heat at the pressure used, it

Y may not be necessary to use brick material,

although this'is preferable. The thickness of the brick protection inside and outside chamber 107 may be varied so as to regulate the amount of heat radiated. The combustion gases,

after assing through the chamber 106, are directe therefrom through the ue 112 into the inside of the chamber 107.' To permit the'inj'ection of said gases in the chamber when superatmospheric pressure is Vmaintained, mechanical means are provided and' interposed in flue 112, such as shown at 113, whereby said gases may be withdrawn from the furnace and compressed to the pressure desired. This mechan- 'ical means is made of material that will resist heat and corrosion.

As af-urther means'to increase the eiciency "of the process, the material which is to be treated therein may be preheated by the heat of the gases `passing through chamber 106,

andv this is effected by positioning in said chamber a preheating coil shown at 114. The

oil to be treated and which is formed of the same materials that have been mentioned here in the description ofthe operation relating to Fig. 1, and which has been made up 1n the same manner, maybe introduced through line 115 into the coil 114 where it is preheated to the proper temperature, preferably short line 116, controlled by valve 117, and' injected into the'upper portion of vertical inner heating chamber 107 through nozzle 118. The

.combustion gases vand the oil combine and `undergo the desired degree of reaction in said chamber after which the vapors, noncondensible gases and combustion gases pass off the to of chamber 107 through line 119, contro led by valve 120.

As has been described in connection with the operation ofthe process in Fig. 1, the degree of. conversion and time element re uired therefor may be controlled by recircu ating portions of products from chamber 1071in controlled manner to said.chamber through line 121, controlled by valve 122, and on which is interposed a recirculating mechanical means 123.

The means illustrated in Fig. 1 for controlling the temperature of the combustion gases at the point where their heat is passed into the oil can also be used in this method of operation, and the partly cooled combustion 'gases can be recirculated from any part of the combustion o f convection chambers 102 or 106, into .the hottest part of the furnacesomewhat close to and in front of the burners 103 and means for doing this are y shown in Figs. 2'and 3 at 124 and 125.

T-he lines 115 and 119 of Figs. 2 and 3 are connected to the balance of the system in the" same manner as shown in Fig. 1. The method of operation of the system, the degree of conversion, the temperature of the gases pass- `ing` through the various parts of the system, and the temperature of the oil when it comes in contact with the combustion action, are all controlled exactly inthe same The incondensible gases-produced in' the system may be passed through an absorption tower (not shown) forl the recovery of any liquid content. Said gases may be sent back to the furnace for use as fuel before or after passing through the absorption tower.

As a further feature" of my invention, water in the form of liquid or vapor may be injected `into the oil undergoing treatment, either into the oil passing through the preheating coil 6, or into fthe heating chamber 8. The steam may be heated to the .required temperature, and in such case may be used as a further means to modify and control the temperature of the materials undergoing treatment in the chamber'8. In other cases. i

it may be desirable to decompose the-steamv before or while it is in contact with the oil,

65 ofconversion from which it is passed through so that the hydrogen and oxygen may enter or producer gas may be injected into the heat-J uated.

verized form,

directly in chemical combination with the oil vapors.

When the oil which is treated contains sul-l phur which forms products which would corrode the system and form objectionable compoundsin the distillates andl gases, I may add to the oil a caustic material such as lime, soda, potash, baryta or the like, either in pulor as an aqueous solution. This caustic material may be added` to the oil before it enters the heating chamber 8.

In this manner, the caustic is brought into intimate contact with the ine particles of the oil atomized through nozzle or perforated pipe 17, and the reaction between the causticv and the sulphur or sulphur compounds is more complete.

In another method of operation, water-gas ing chamber 8, or at any point in the passage of combustion gases through theurnace l,

whereby additional reaction will occur, causproducer gas andlfor ing enrichment of the mation of aromatic, ethylenic, alklyl com` pounds and the like.

fore a process wherein all of the combustion gases formed in the furnace are brought in contact with the oil to be treated for heating and converting it, it is lunderstood that only a part of the combustion gases formed may be so utilized. .In this case, a by-pass flue to the stack is branched on the iues 7 and 112 and suitable dampersfare provided to control the proportion of combustion gases evac- I claim as my invention 1. A process for convertingliquid hydrocarbons, which com rises raising the temperature of said liquld hydrocarbons by subjection to indirect heat conductive relationship with combustion gases, in subsequently introducing the heated hydrocarbons into direct contact with saidlpcombustion -gases to cause substantial vaporization, in removing said vapors and subjecting same to cracking reaction in a'n enlargedreaction zone, in removing vapors from said reaction -zone and subjecting same to dephlegmation, in remov- ,ing the reiiux condensate fromI said dey tentsof said zones in the .combustion gases,

which comprises generating combuscontact 'with said combustion gases to cause substantial vaporizatlon, 1n removing sald vapors and subjecting same to cracking reaction in an enlarged reaction zone, in removbustion gases regulated portions of the vapors'passlng to theenlarged reaction zone, and in regulating temperature conditions within the gas generating zone by locally recirculating therethrough regulated portions of the combustion gases.

3. `A process of hydrocarbon oil conversion consisting in heating the oil in indirect con-1 tact with ygases of combustion in a heating zone, passing the heated oil and gases of combustion Vinto a second heating zone in direct physical contact to vaporize the oil, and recirculating regulated'portions of the resultant c mixture vof vapors and gases in `a local cycle While I have shown and described heretopassing the heated oil and gases of combustion into a `second zone in direct physical contact attended byvaporization of the oil, and recirculating` regulated 4portions of the cona local cycle respectively through'each of said zones.

5. procesmsfor cracking hydrocarbon oil which comprises first heating the oil by passing the same through a heating zone in indirect heat conductive relationship with hot combustion gases, discharging the .heated oil from said heating zone into a conversion zone maintained under cracking conditions of temperature and causing the oil to mingle with said combustion gases in said conversion zone thereby removing vaporous products of the cracking and combustlon gases from said conversion zone, and returning a portion of the removed vaporous products and combustion gases directly to said conversion zone without passage through said heating zone. p

6. Aprocessfor cracking hydrocarbon oil el'ecting cracking of the oil, i

which comprises rst heating the oil by pass` ing the same through a heating zone in indirect'heat conductive relationship with hot Y discharging the heated oil from said heating zone into a. conversion zone maintained under cracking vconditions of temperature andi causing the oil to mingle with said combustion gases in said converslon zone thereby effecting cracking of the oil, removp ing vaporous products of the cracking and combustion gases from said conversion zone,y returnlng a portion of the removed vaporous products and combustion gases directly to said conversion zone without passage through said heating zone, dephlegmating vapors re- `movcd from said conversion zone thereby 5 forming reux condensate, and returning said condensate to the process for retreatment.

7. A process for cracking hydrocarbon oil 'which comprises generating hot combustion 1 gases at a point remote from the oil to be cracked, passing the oil in indirect heat conductive relationship with said combustion gases, then bringing al1 ofthe oil thus .heated into direct physical contact with said com- 15 bustion gases under cracking conditions of temperature in a conversion zone and thereby v eiecting cracking of the oill, removing vapors and gases from said zone, and continuously returning a portion of the removed vapors and gases directly to said zone. y

8. A hydrocarbon oil conversion rocess which comprises cracking the oil by irectly 'contacting the same with agase'ous heating e medium in av conversion zone, removin the vresultant mixture of vapors 4and gases rom said zone, and recirculating regulated portions of said mixture in a local cycle through sald zone. y

9. A hydrocarbon oil conversion rocess which comprises cracking the oil by irectly contacting the same with hot 'combustion' gases in a conversion zone, removing the resultant mixture of vapors and 'gases from said gzlone, and recirculating regulated -portions of said mixture in a localcycle through said zone. 1

. In testimony whereof I aix my signature.

' CARBON P. DUBBS. 

